JPS6059346B2 - Fiber processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for treating textile fibers, and in particular to a method for improving the stain resistance of said fibers.

It is known to treat textile fibers to impart stain resistance.

For example, British Patent No. 117512@ describes a fibrous material with the unit formula RSlOl. Solid silsesquioxane represented by 5 (
In the formula, 5 to 100% of R is a hydrocarbon having a substituent containing 1 to 7 carbon atoms, where the substituent is an amino group, a mercapto group, a hydroxyl group, an epoxy group, an acrylate group, a methacrylate group, or a cyano group. group or carboxy group,
Improved anti-slip, anti-slip properties by treatment with a colloidal suspension of monovalent hydrocarbon radicals of 1 to 7 carbon atoms or halogenated derivatives thereof, in which up to 95% of the R groups are monovalent hydrocarbon radicals of 1 to 7 carbon atoms or halogenated derivatives thereof. and/or imparting dust stain prevention properties. However, in addition to the dust staining properties mentioned in the said British patent, fibrous materials are also susceptible to staining by oily substances.

For example, while wearing clothing products become soiled by secretions from the human body and food products. Additionally, products are also contaminated by machine oil during processing of fibers, such as during cloth manufacturing. Such stains cannot be removed easily unless they are removed immediately. In some cases, soil removal is made more difficult if the fibers have been previously treated with silicone to impart certain desirable properties, such as lubricity and soft contact. This problem was solved in British Patent No. 136, which disclosed that the stain removability of fibers could be improved by applying a water-soluble polymer of polymethylsiloxane and an unsaturated carboxylic acid together.
No. 7666. We have found that oily soils can be easily removed from textile fibers if the fibers are treated with certain organosiloxanes in which certain quaternary ammonium bases are present.

U.S. Pat. No. 4,005,030, U.S. Pat. No. 4,005,117 and U.S. Pat. It is known from No. 4006176. It is theorized that this resulting advantage results from the formation of a thin siloxane coating on the surface. However, this invention relates to improving the removal of oil-based soils from textile fibers that have been treated with additional siloxanes for the purpose of obtaining other properties such as soft feel, lubricity, crease recovery, etc. It is. According to this invention, at least one -0M group (M is a hydrogen atom, an alkyl group, or an alkoxyalkyl group) bonded to silicon in the molecule, and a general formula [wherein R represents carbon, hydrogen, and optionally oxygen and the oxygen exists in the form of an ether bond and/or a hydroxyl group.
A divalent group containing one carbon atom, R'' is a monovalent hydrocarbon group having 1 to 15 carbon atoms or a group -(0Q)80
Z (wherein Q is an alkylene group of 2 or 3 carbon atoms, a has a value of 1 to 20, and z is a hydrogen atom, an alkyl group or an acyl group), each R'' is a methyl group or an ethyl group,
a polydiorganosiloxane having at least one quaternary base bonded to a silicon atom represented by A method of treating fibers is provided which comprises applying to the fibers a polydiorganosiloxane in which the remaining substituents which may remain are monovalent hydrocarbon groups of 2 to 8 carbon atoms.

The above-described polydiorganosiloxanes used in the process of this invention are linear or substantially linear siloxane polymers containing at least one silicon-bonded 0M group per molecule, such as -0H, -0CH3, 0C4H9 or one (
0CI-! 2,CH2,0CH3) group.

Preferably, the 0M group herein has up to about 6 carbon atoms. Furthermore, the -0M group may be present anywhere on the siloxane chain, including the terminal silicon atom. The divalent group R in the quaternary salt having the above general formula consists of carbon and hydrogen, or carbon, hydrogen and oxygen, and oxygen exists in the form of an ether bond and/or a hydroxyl group. R groups are thus, for example, methylene, ethylene, hexylene, xenylene, -CH2CH2OCH2CH2- and -(CH2
)20-CH2CHOHCH2 group, preferably R
is one (CH2)3-, -(CH2), - or CH2C
It is one H-CH3.CH2 group. The R'' group is any monovalent hydrocarbon group having 1 to 1 carbon atoms, such as an alkyl group such as a methyl, ethyl, propyl, butyl or tetradecyl group; an alkenyl group such as a vinyl group; or an aryl group; alkaryl or aralkyl groups such as phenyl, naphthyl, tolyl, 2-ethylphenyl, benzyl and 2-phenylpropyl groups.The R'' group may be a -(0Q)AOZ group as defined above; An example of this group is 1(0CH2CH2)0H, -(0C
H2CH2)3,1(0CH2CH2)3-(0CH2
CH2CH2)30C4H9 and -(0CH2CI(2
)20C3H7. X is preferably chlorine or bromine. At least 40% of the total silicon substituents in the polydiorganosiloxane are methyl groups; other substituents that may be present besides the methyl groups are quaternary bases and monovalent hydrocarbons of 2 to 8 carbon atoms. Groups such as propyl, vinyl or phenyl groups. For most applications, quaternary bases and -0
Preferably, substantially all substituents present in addition to the M group are methyl groups. At least one quaternary base should be present in the polydiorganosiloxane molecule. The actual proportion of quaternary base for a particular treatment will depend on factors such as the degree of stain resistance desired and the application conditions. For example, if low deposition on fibers is desired, polydiorganosiloxanes with a high proportion of quaternary bases may be used in combination with other silicon treatments such as those described below. It is preferable to use On the other hand,
If properties such as lubricity and soft feel resulting from substituents other than quaternary bases such as methyl groups are desired, high molecular weight polydiorganosiloxanes with relatively low proportions of quaternary bases may be used. It is preferable to use Polydiorganosiloxanes can be made by any suitable method, including suitable cyclic siloxane equilibration.

However, polydiorganosiloxanes are silanol-terminated polydiorganosiloxanes such as polydimethylnosiloxanes with the general formula (wherein each Y is a monovalent hydrocarbon group, preferably a methyl group or preferably up to 6 alkoxy groups or alkoxyalkoxy groups, with fewer Both Y groups are an alkoxy group or an alkoxyalkoxy group, and R, R″
, R'' and X have the same meanings as above).

In the practice of this invention, polydiorganosiloxanes may be used as the only active ingredient in the coating composition;
Or you can use them with other ingredients. For example, polydiorganosiloxane treatment compositions may adhere to fibers,
Catalysts and/or crosslinking agents may be included to effect or facilitate crosslinking or chain extension of the polydiorganosiloxane onto the fibers. Catalysts and crosslinking agents suitable for such reactions are well known in the art and include metal organic compounds such as tin carboxylates, titanates and titanium chelates as catalysts and polyfunctional silicone compounds such as alkoxy Silane, partial hydrolyzate of alkoxysilane, oxime silane and SH
Examples include polysiloxanes having groups such as poly(methylhydrogen)siloxane. We have also found that improved and advantageous soil removal properties are obtained when using the quaternary base-substituted polydiorganosiloxanes described above in combination with other organosilicon fiber treatments.

Thus, the loss of oil stain resistance resulting from siliconization of the fibers can be at least reduced by the use of the polydiorganosiloxanes described above. According to another aspect of the invention, the above-mentioned polydiorganosiloxane is combined with one or two of the above-mentioned specific quaternary base-free polydiorganosiloxanes.
A method of treating fibers is provided which comprises treating fibers in combination with one or more organosilicone compounds.

The application of the polydiorganosiloxane can be carried out before, simultaneously with, or after the application of the organosilicone compound. Application of the polydiorganosiloxane and organosilicone compound may be carried out in two separate treatments if appropriate, but it is preferred to avoid these two separate treatment steps and apply them together. . The polydiorganosiloxane can be used with any of the organosilicone compounds applied to the fiber to impart desired properties to the fiber.

Such desirable properties include, for example, lubricity, soft feel, and wrinkle resistance. The organosilicone compound may be a silane, but more commonly it is an organoloxane, in particular at least about 50% of the total silicon-bonded substituents are methyl groups, with the remaining substituents that may be present being other substituents. Monovalent hydrocarbon groups such as higher alkyl groups such as tetradecyl and octadecyl groups, phenyl groups, vinyl groups and allyl groups, and monovalent hydrocarbon oxy groups (hydrocarbonoxy groups) and hydrocarbon groups with substituents, such as These include alkoxy groups, alkoxyalkoxy groups, fluoroalkyl groups, hydroxyalkyl groups, aminoalkyl groups and polyamino(alkyl) groups, mercaptoalkyl groups and carboxyalkyl groups. Examples of such hydrocarbon oxy groups and hydrocarbon groups having substituents are methoxy group, ethoxy group, butoxy group, methoxyethoxy group, 3,3-
These include trifluoropropyl group, hydroxymethyl group, aminopropyl group, β-aminoethyl-γ-aminopropyl group, mercaptopropyl group, and carboxybutyl group. In addition to the organic substituents mentioned above, organosilicone compounds may have silicon-bonded hydroxyl groups, which are usually present on terminal silanol groups or present in polydiorganosiloxanes, or It may also have hydrogen atoms bonded to silicon, such as in poly(methylhydrogen)siloxane or in copolymers of dimethylsiloxane units with methylhydrogensiloxane units and/or dimethylhydrogensiloxane units. In some cases, the organosilicone compounds may be of two or more different types.

For example, it applies to both silanol-terminated polydimethylsiloxanes and their crosslinkers, such as poly(methylhydrogen)siloxanes, alkoxysilanes such as CH3Si(0CH,)
, and/or NH2CI(,CH2NH(CH2)3
Included are Si(0C2H5)3 or partial hydrolysis products, and condensates of such silanes. Organosilicon compounds therefore also include silanes or siloxanes that serve as crosslinking agents for polydiorganosiloxanes. Thus, a wide variety of organosilanes and/or organosiloxanes can be used as organosilicone treatments depending on the properties desired in the treated fibers. The use of organosilicone compounds for the treatment of textile fibers is well known, for example British Patent Nos. 1011027 and 1230.
No. 779, No. 1425858, No. 1429263,
No. 14857, No. 1491747 and No. 1552
It is written in 35 inches. The polydiorganosiloxane and organosilicone compounds can be applied either separately or as a mixture of the two by any suitable application technique, such as by fully dipping the fibers or by kiss rolling.

They may be applied using an organic solvent carrier;
Alternatively, it may be applied as an aqueous dispersion or emulsion. The proportion of quaternary salt polydiorganosiloxane used will depend on the degree of stain resistance required, the proportion of quaternary base present in the siloxane, and the presence or absence of other organosilicon treating agents. It can vary widely depending on factors.

It is generally preferred to apply 0.2 to 2% by weight of polydiorganosiloxane, based on the weight of the fibers. but,
Ratios outside this range can also be used if desired. That is, even the application of small amounts of polydiorganosiloxane, such as 0.1% by weight, provides useful improvements in stain resistance. However, increasing the application rate to application levels greater than about 4% by weight does not significantly improve this property further. When polydiorganosiloxanes are applied together with other organosilicone treatments, the relative proportions of the two treatments can vary over a wide range depending on the same factors as when applying polydiorganosiloxanes alone. . The above relative proportions also depend somewhat on the degree to which the polydiorganosiloxane contributes to the properties imparted to the fiber by the organosilicone treatment agent. If such a contribution is possible, the proportion of organosilicone treatment agent can be lowered and the desired effect restored by increasing the proportion of polydiorganosiloxane. However, in general, the total coverage of polydiorganosiloxane and organosilicone treatment agents is about 5-6% based on the weight of the fiber.
It never exceeds. After applying the polydiorganosiloxane to the fibers, the applied composition is suitably cured at ambient temperature or by heating. It is generally preferred to subject the fibers to temperatures in the range of about 100C to 20C after treatment. The method of the invention can be used to treat a variety of fibers, such as cotton, polyester, acrylic and nylon.

The fibers can be processed in any form, such as monofilaments, threads, random fibers, fabrics, and finished products. In addition to imparting improved soil removal properties to fibers treated according to this invention, the fibers also exhibit useful improvements in antistatic properties. This invention will be explained below with reference to examples, where parts in the text mean parts by weight.
means a methyl group.

Example 1 411 parts of a silanol-terminated polydimethylsiloxane having an average of about 11 dimethylsiloxy units per molecule and Me
(MeO)2Si(CH2)3N+Me2(Cl3H2
7) Combine C1-204 parts at 150°C for 6 hours under nitrogen.
heated to.

The volatiles generated during this reaction were removed under reduced pressure. The reaction product was a water-soluble, amber-colored, liquid polydimethylsiloxane containing methoxy groups and a quaternary base bonded to each terminal silicon atom. Desized and refined 65%/35
% cotton/polyester woven fabric was padded with a solution containing the siloxane prepared as described above, MeSi''(0Me)3, and dibutyltin di(laurinthioglycolate).The fabric was then dried in one powder at 80°C, and ℃3
The applied siloxane was cured by heating. The application conditions were 1% siloxane and MeSi (0CH3) on the treated fabric.
The conditions were such that 30.25% and 0.06% of tin were deposited. The ease with which oil stains can be removed from treated fabrics was evaluated by separately depositing 0.5 mt each of molten butter, liquid paraffin, olive oil, and mayonnaise onto pieces of fabric.

The soil was allowed to set for 1 hour and the resulting soiled fabric pieces were washed in an automatic household washing machine (1800 g load, polyester/cotton program, 150 g detergent). After spin drying, the degree of stain removal was determined by comparison with an AATCC stain removal replica (.AATCC Test 130:1977). The samples were then washed an additional five times and the soil removal measurement test was repeated. The test results are listed in the table below.

The numbers shown in the table range from 1 (no dirt is removed) to 5.
(The stain was completely removed). The fold restoration angle is BS3O86 before and after 5 wash cycles:
1972 on each sample and obtained the following results: Example 2 MeSi (CMe), trimethylsiloxy-terminated poly(
The procedure of Example 1 was repeated except that methylhydrogen)siloxane was substituted.

The concentrations used were such that the amount of polydiorganosiloxane deposited was 2% by weight, the amount of poly(methylhydrogen)siloxane deposited was 0.1% by weight, and the amount of the tin compound deposited was 0.0% by weight. The soil removal values after one wash are as follows.

Example 3 Example 1 except that the polydimethylsiloxane reactant contained an average of about 8 dimethylsiloxy units per molecule.
A quaternary salt-containing polydiorganosiloxane was prepared in the same manner as above.

7 (1) parts of this polydiorganosiloxane and 37 parts of silanol-terminated polydimethylsiloxane [molecular weight Mn 74O]
0 parts were combined and heated at 150° C. for 4 hours in the presence of 1% by weight of dibutyltin dilaurate. Volatiles were removed under reduced pressure. The resulting product has the following theoretical structural formula: (wherein, B is 1(CH2)3N+Me2Cl3H27C
The viscosity at 250°C is 350
It was an amber liquid with a weight of 0.00 centistokes (CS).

This copolymer was prepared as MeSi(0Me) as described in Example 1.
3 and dibutyltindi(lauryl thioglycolate) and applied to a piece of 65%/35% cotton/polyester woven fabric to obtain the same coverage as in Example 1 (Sample A).
. For comparison, a piece of cotton/polyester woven fabric (Sample B) was treated similarly, except that the copolymer was replaced with a silanol-terminated high molecular weight polydimethylsiloxane. The soil removability of these samples and untreated fabrics was determined as in Example 1 after staining and washing five times.

Claims (1)

[Scope of Claims] 1 At least one silicon-bonded -OM group (M is a hydrogen atom, an alkyl group, or an alkoxyalkyl group), and a general formula ▲ a mathematical formula, a chemical formula, a table, etc. ▼ [In the formula R consists of carbon, hydrogen and optionally oxygen, the oxygen being a divalent group containing 3 to 10 carbon atoms present in the form of an ether bond and/or a hydroxyl group; R' is a divalent group containing 1 to 15 carbon atoms;
monovalent carbon hydrogen group or group -(OQ
)_aOZ (in the formula, Q is 2 or 3 alkylene groups,
a has a value of 1 to 20, Z is a hydrogen atom, an alkyl group or an acyl group), each R'' is a methyl group or an ethyl group, and X is a halogen atom]. A polydiorganosiloxane having one quaternary base, in which at least 40% of the total silicon-bonded substituents in the polydiorganosiloxane are methyl groups, and the remaining substituents that may be present range from 2 to 8. A method for treating fibers comprising applying to the fibers a polydiokanosiloxane which is a monovalent carbon hydrogen group of carbon atoms. 2. Claim 1, wherein M is a hydrogen atom or an alkyl group of 6 or less carbon atoms. The method described in Section 3. 3 R is -(CH_2)_3-, or -(CH_2)
_4- or -CH_2CH・CH_3CH_2-, the method according to claim 1 or 2. 4 Polydiorganosiloxane is silanol-terminated polymethylsiloxane with the general formula ▲ Numerical formulas, chemical formulas, tables, etc. The following Y is a methyl group, R is a divalent group containing 3 to 10 carbon atoms, consisting of carbon, hydrogen and optionally oxygen, where the oxygen is present in the form of an ether bond and/or a hydroxyl group, R' is a monovalent carbon hydrogen group having 1 to 15 carbon atoms or a group -(OQ)_aOZ (wherein Q is an alkylene group having 2 or 3 carbon atoms, and a has a value of 1 to 20; Z is a hydrogen atom, an alkyl group or an acyl group)
, each R'' is a methyl group or an ethyl group, and X is a halogen atom. The method according to any one of claims 1 to 4, wherein a siloxane curing catalyst is also applied.6 At least one silicon-bonded -OM group (M is a hydrogen atom, an alkyl group or an alkoxyalkyl group) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. Divalent group containing a carbon atom, R' is 1 to 15
monovalent carbon hydrogen group or group -(OQ
)_aOZ (in the formula, Q is 2 or 3 alkylene groups,
a has a value of 1 to 20, Z is a hydrogen atom, an alkyl group or an acyl group), each R'' is a methyl group or an ethyl group, and X is a halogen atom]. A polydiorganosiloxane having one quaternary base, in which at least 40% of the total silicon-bonded substituents in the polydiorganosiloxane are methyl groups, and the remaining substituents that may be present range from 2 to 8. Polydiorganosiloxane, which is a monovalent carbon hydrogen group of carbon atoms, is applied to the fiber before, at the same time, or after applying to the fiber one or more organosilicone compounds that do not have a quaternary base. 7. The method according to claim 6, wherein M is a hydrogen atom or an alkyl group of 6 or less carbon atoms. 8. R is -(CH_2)_3-, or -(CT_2 )
_4- or -CH_2CH・CH_3CH_2-, the method according to claim 6 or 7. 9 Polydiorganosiloxane is silanol-terminated polymethylsiloxane with the general formula ▲ Numerical formulas, chemical formulas, tables, etc. The following Y is a methyl group, R is a divalent group containing 3 to 10 carbon atoms, consisting of carbon, hydrogen and optionally oxygen, where the oxygen is present in the form of an ether bond and/or a hydroxyl group, R' is a monovalent carbon hydrogen group having 1 to 15 carbon atoms or a group -(OQ)_aOZ (wherein Q is an alkylene group having 2 or 3 carbon atoms, and a has a value of 1 to 20; z is a hydrogen atom, an alkyl group or an acyl group)
, each R'' is a methyl group or an ethyl group, and X is a halogen atom] The method according to any one of claims 6 to 8. 10. A method according to claim 6, in which the compound is applied to the fiber simultaneously with the polydiorganosiloxane. 11. A method according to any one of claims 6 to 10, in which the fiber is also applied with a siloxane curing catalyst.